Perfumes including perhydro 1,4,9,9-tetramethyl-4,7-methanoazulenones

ABSTRACT

PERHYDRO 1,4,9,9-TETRAMETHYL - 4,7 - METHANOAZULENONES USEFUL AS OLFACTORY AGENTS; AND PERFUME COMPOSITIONS CONTAINING SUCH AZULENONES.

United States Patent 3,748,284 PERFUMES INCLUDING PERHYDRO 1,4,9,9-TETRAMETHYL-4,7-METHANOAZULENONES James D. Crossman, 01d Bridge, BrajaD. Mookherjee, Matawan, Robert S. de Simone, Madison Township, County ofMiddlesex, and Ernest T. Theimer, Rumson, N.J., assignors toInternational Flavors & Fragrances Inc., New York, N.Y.

No Drawing. Original application June 10, 1968, Ser. No. 735,544, nowPatent No. 3,679,749. Divided and this application Nov. 26, 1971, Ser.No. 202,598

Int. Cl. A61k 7/00; C07c 49/ 27; Cllb 9/00 U.S. Cl. 252-522 3 ClaimsABSTRACT OF THE DISCLOSURE Perhydro l,4,9,9-tetramethyl 4,7methanoazulenones useful as olfactory agents; and perfume compositionscontaining such azulenones.

This application is a division of application Ser. No. 735,544, filed onJune 10, 1968, now US. Pat. 3,679,749.

BACKGROUND OF THE INVENTION Materials which can provide amber and woodyfragrance notes are known in the art of perfumery. Many of the naturalmaterials which provide such fragrances and contribute desired nuancesto perfume compositions are high in cost, variable in quality from onebatch or crop to another, and/or are generally subject to the vagariesof natural products.

There is accordingly a continuing effort to find synthetic materialswhich will replace the essential fragrance notes of perfumecompositions, but many of these synthetic materials either have thedesired nuance only to a relatively small degree or else contributeundesirable or unwanted odors to compositions. Buchi et al., 83 J.A.C.S.927 (1961), shows the production of a material called patchoulione whichis stated to be octahydrol,4,9,9-tetramethyl-3a,7-methanoazulen-5 4H)-one.

THE INVENTION having the formula R 5 a d) wherein one of R R and R isoxygen and each of the other two represents two hydrogen atoms. It alsorelates to the use of these ketones as olfactory agents and in perfumecompositions. The novel azulenones of the present invention provide asuperior amber, precious wood, camphoraceous fragrance note and are muchmore intense than those previously known. Accordingly, smallerquantities can be used to impart a woody amber fragrance to perfumecompositions and to perfumed articles, such as soap, face powder andother articles as disclosed hereinafter.

3,748,284 Patented July 24, 1973 I II It will be appreciated that theforegoing structures include the various stereoisomeric forms.

I and II can be used individually or in admixture with each other orwith III. Generally, III is utilized in admixture with the other twonovel materials, and in many aspects of the present invention a mixtureof the three ketones is preferred.

The ketones of this invention are useful as olfactory agents andfragrances. They have a camphoraceous woody amber fragrance in their ownright and can impart this fragrance note to perfume compositions andperfumed articles according to the present invention. They can either beformulated into, or used as components of, perfume compositions.

The term perfume composition is used herein to mean a mixture of organiccompounds, including, for example, alcohols, aldehydes, ketones, estersand frequently hydrocarbons which are admixed so that the combined odorsof the individual components produce a pleasant or desired fragrance.Such perfume compositions usually contain: (a) the main note or thebouquet or foundation-stone of the composition; (b) modifiers whichroundoff and accompany the main note; (c) fiXatives which includeodorous substances which lend a particular note to the perfumethroughout all stages of evaporation, and substances which retardevaporation; and (d) top-notes which are usually low-boilingfresh-smelling materials.

In perfume compositions the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effect of each ingredient.Thus, the individual compounds of this invention, or mixtures thereof,can be used to alter the aroma characteristics of a perfume composition,for example, by highlighting or moderating the olfactory reactioncontributed by another ingredient in the composition.

The amount of mixtures or compounds of this invention which will beeffective in perfume compositions depends on many factors, including theother ingredients, their amounts and the effects which are desired. Ithas been found that perfume compositions containing as little as 2% byweight of mixtures or compounds of this invention, or even less, may beused to impart a fine woody amber odor to soaps, cosmetics and otherproducts. The amount employed can range up to 7% or higher and willdepend on considerations of cost, nature of the end product, the effectdesired on the finished product and the particular fragrance sought.

The azulene ketones described herein can be used alone or in a perfumecomposition as olfactory components in detergents and soaps; spacedeodorants; perfumes; colognes; bath preparations such as bath oil, bathsalts; hair preparations such as lacquers; brilliantines, pomades, andshampoos; cosmetic preparations such as creams, deodorants, handlotions, sun screens; powders such as talc, dusting powders, facepowder; and the like. When used as an olfactory component of a perfumedarticle, as little as 3 0.011 of the novel *ketone will sufiice toimpart an amber, camphoraceous woody odor.

In addition, the perfume composition can contain a vehicle or carrierfor other ingredients. The vehicle can 'be a liquid such as alcohol,glycol, or the like. The carrier can be an absorbent or adsorbent solidsuch as a gum or components for encapsulating the composition.

The examples which appear hereinbelow illustrate perfume mixtures, soapand other formulations within the scope of this invention. It is to beunderstood that these compositions are preferred examples, and theinvention is not to be considered as restricted thereto except asindicated in the appended claims.

The ketones of this invention can be prepared by a novel process whichcomprises treating a saturated alcohol having the structure or mixturesof such alcohols wherein one of R R and R is OH and the other two are Hwith an agent which will oxidize a secondary hydroxyl to a carbonyl andprovide the novel ketones having the structure wherein R R and R are asdisclosed above.

More specifically, the perhydro alcohol or alcohols are oxidized to aketone by a strong oxidizing agent such as chromium trioxide, analkali-metal dichromate such as potassium dichromate, sodium dichromateand the like, or an alkali-metal permanganate such as potassiumpermanganate and the like. It will be understood that the oxidin'ngagent and conditions used are such as to convert the secondary hydroxylgroup to the carbonyl group without further oxidizing the hydrocarbon.

This secondary hydroxy-to-carbonyl reaction is preferably carried out inthe presence of a chromium trioxide catalyst because of its relativemildness and specificity.

The reaction is carried out under acidic conditiOns. Thus, inorganicacids such as sulfuric acid and the like or organic acids such as loweraliphatic acids like acetic acid can be used to provide the acidicreaction milieu. There is also preferably a reaction vehicle such as anaqueousv vehicle present to permit moderation and control of thereaction and to facilitate contact of the oxidizing agent 'with thesecondary alcohol.

A temperature is maintained sufiicient to provide a satisfactory rate ofoxidation while avoiding further oxidation beyond the alcohol. It hasbeen found that the reaction can be carried out at temperatures of from5 C. to the reflux temperature of the aqueous reaction system. It isgenerally preferred to carry out the oxidation at temperatures on theorder of 20-30 C. since this provides an acceptable reaction rate andminimizes side reactions.

The reaction can be carried out under atmospheric or suborsuperatmospheric pressures. However, because of the moderate temperaturerequirement of the reaction, atmospheric pressure is suitably used.

The novel ketones of this invention are conveniently prepared frombeta-patchoulene having the structure or delta-patchoulene having thestructure (1,4,9,9,-tetramethyl-A octahydro-4,7-methan0azulene) byconverting these materials to the saturated alcohols and then oxidizingthe alcohol to the ketones as disclosed above. One method of obtainingthe alcohol is by a direct oxidation of the patchoulene to provide theunsaturated ketones, as described in the copending application of BrajaD. Mookherjee, entitled Novel Process and Product, Ser. No. 735,545filed June 10, 1968, now U.S. Pat. 3,679,750 herewith, and thenhydrogenating the unsaturated ketones to produce the saturated alcohols.A novel method for preparation of the alcohols according to the presentinvention comprises treatment of the patchoulene with a diborane sourceto form a boron addition compound and then oxidizing and hydrolyzing therearranged addition compounds to provide the secondary alcohols.

The novel ketones of the present invention can also be produced frompatchouli alcohol, stated by Buchi et al., 86 J.A.C.S. 4438 et seq.(1964) to have the structure awn-s This alcohol is dehydrated under acidconditions to delta patchoulene. beta-Patchoulene is readily preparedaccording to the method of Bates and Slagel, 84 J.A.C.S. 1307 (1962).

The preparation of the monounsaturated methanoazulenone has beendescribed in the aforesaid copending application Ser. No. 735,545. Themonounsaturated methanoazulenone produced by the process can berepresented by the following structure:

wherein one of the dashed lines is a double bond and the other twodashed lines are single bonds, and one of R and R is oxygen and theother represents two hydrogen atoms.

The double bond of the methanoazulenone is hydrogeenated and the ketogroup is simultaneously converted to a secondary alcohol group. Thehydrogenation to obtam the secondary alcohol can be carried out withgaseous hydrogen in the presence of a hydrogenation catalyst such asRaney nickel, palladium on carbon, and the like. The reduction can alsobe performed using an alkali-metal reduction process which utilizessodium or other alkalimetal amide. It will be understood that thealkali-metal amide reduction can also be carried out by the use of anammonium hydroxide system containing an alkali-metal such as sodium anda lower alkanol such as ethanol and the like.

The hydrogenation of the monounsaturated methanoazulenone is carried outat a temperature sufiicient to afford a reasonable reaction rate. Forthe alkali-metal amide reduction, substantial molar excesses of alcohol,alkali-metal and ammonium hydroxide are used, based on the quantity ofmethanoazulenone. Thus, ten or more moles of ammonium hydroxide and twoto four moles of alkali-metal are used. It will be understood thatsodium amide in alcohol can also be used in the same relativeproportions as set forth above. The amide reduction process ispreferably carried out at temperatures ranging from 0 to about 30 C.

According to a novel process, the perh'ydro secondary alcohol can alsobe prepared directly from betaatchoulene, described above, by treatmentwith a diborane source to form the boron addition compound and oxidationand hydrolysis to form the aforesaid rearranged secondary alcohol havingthe formula in an acidic reaction medium to form a methano bridge.Bulnesol is conveniently obtained from guaiacwood oil. The cyclizationis carried out by treating the bulnesol or bulnesol fraction ofguaiacwood oil with p-toluenesulfonic acid and formic acid in a vehiclesuch as toluene. The mixture is heated at reflux until evolution ofwater ceases. The reaction mixture is then neutralized with alkali suchas an alkali-metal hydroxide and distilled to obtain thebeta-patchoulene.

beta-Patchoulene is treated with a diborane source such as diboraneitself, an alkali-metal boro-hydridealuminum chloride mixture, analkali-metal boro-hydrideboron trifiuoride mixture, and the like. Thealkali metal borohydride sources of diborane which can be used includelithium borohydridealuminum chloride, sodium borohydride-borontrifiuoride, and the like. The reaction is desirably carried out in aninert vehicle in which diborane is soluble to facilitate control of thereactants, lower the reaction pressure, and permit moderation andcontrol of the reaction. It will be understood by those skilled in theart that the formation of the boron adduct is to be carried out in asubstantially water-free environment. Suitable reaction vehicles for usein the hydroboration reaction include high-boiling ethers such astetrahydrofuran, dimethoxyethane, diglyme, and the like.

As noted above, the diborane can be supplied to the reaction eitherdirectly in the gaseous form or as a diborane-producing mixture such asalkali-metal borohydride-boron trifiuoride. A preferred mixture issodium borohydride-boron trifluoride.

In carrying out the reaction, it has been found that the proportions ofbeta-patchoulene and diborane can be varied over a range. Thus,equivalent quantities of patchoulene and diborane can be used incarrying out the process. It will be understood that, when a complexfurnishing diborane to the reaction is used, the quantity of the complexwhich can be used is that required to provide the desired proportion ofdiborane in the reaction. Generally, it is preferred that an excess ofthe diborane by present in the reaction mixture to assure completereaction of the patchoulene and isomerization of the initially formedtertiary adduct. The formation of the boron adduct from patchoulene ispreferably carried out at temperatures of 65 C. to C.

After the boron adduct has been prepared, it is oxidized and hydrolyzedto the perhydro secondary alcohol shown above. Those skilled in the artwill appreciate from the present description that the oxidation andhydrolysis can be carried out sequentially or substantiallysimultaneously in a single reaction mixture. The oxidation of the boronadduct is carried out through the use of a relatively strong oxidizingagent. Suitable oxidizing agents for this step of the process includehydrogen peroxide and acid-di chromate media. Hydrogen peroxidestrengths of from about 20 to about 60% are preferred. When anaciddichromate medium is utilized, the acid is preferably a stronginorganic acid such as sulfuric and the chromate is provided by chromictrioxide or an alkali-metal dichromate such as potassium dichromate andthe like. All percentages, parts, proportions and ratios herein are byweight, unless otherwise indicated.

The oxidation reaction is carried out at temperatures which afford agood reaction rate while minimizing undesirable side reactions. Thus,when hydrogen peroxide is used as an oxidizing agent to form theperhydro secondary alcohol, temperatures on the order of from 20 to 40C. are used. When an acid-dichromate medium is used, the temperaturescan range from 15 C. to 40 C. The time for carrying out the reaction canvary, and it has been found that good yields are obtained in /2 to 2hours.

The hydrolysis to provide secondary alcohols is pref erably carried outwith a strong base. Examples of preferred strong bases are thealkali-metal hydroxides such as sodium hydroxide, potassium hydroxide,and the like. When hydrogen peroxide is the oxidizing agent, the basecan be added to the boron adduct before the treatment with peroxide.

For convenience, the perhydro alcohol obtained when R is hydroxyl willbe referred to as 3-ol; when R is hydroxyl, 2-01; and when R ishydroxyl, 8-01. The proportion of each of these isomers obtained byhydroboration and oxidation-hydrolysis of beta-patchoulene variesaccording to the concentration of the reactants, the temperature of thehydroboration reaction, and to a lesser extent the time of reaction andwhether the reaction is performed by adding oxidation agents directly tothe hydroboration reaction mixture or whether a separation is firstperformed. It has been found in carrying out the process of thisinvention that the 2-01 is generally the major product, the 3-01 isobtained in lesser amounts, and the 8-01 is obtained in relatively smallquantities. It will be appreciated that the oxidation of the secondaryalcohol to provide the perhydro ketone will generally provide theketo-isomer corresponding to the secondary alcohol isomer. For instance,oxidation of the 2-01 provides the corresponding 2-one (II).

Depending upon the particular isomer or isomer mixture of ketonesprepared accordnig to this invention, the intermediate products, e.g.,the boron adduct, the monounsaturated methanoazulenone, the perhydrosecondary alcohol, can be purified and/or isolated as desired.Alternatively, purification and/ or isolation can be carried out on thefinal perhydro ketone product. At least the final perhydro ketone isdesirably purified to remove unreacted materials, by-products, colorbodies, foreign odor bodies, and the like. The purification and/orisolation of the intermediates and the final ketonic products can becarried out by conventional techniques. Thus, the intermediate and finalproducts can be purified, separated, and/or isolated by distillation,extraction, preparative chromatographic techniques, and the like.

The ketones obtained according to this invention have an amber, preciouswood fragrance note. This fragrance note is quite intense, andrelatively small quantities of the ketones according to this inventionconfer such a fragrance note on perfumed articles, perfume compositionsand other olfactory agents. Moreover, the novel ketones herein disclosedmaintain substantially the same fragrance note over a period of time ona blotter, so that formulation of olfactory agents is facilitated andsimplified.

The following examples are given to illustrate embodiments of theinvention as it is presently preferred to practice it. 'It will beunderstood that these examples are illustrative and the invention is notto be considered as restricted thereto except as indicated in theappended claims.

EXAMPLE -I Hydroboration of beta-patchoulene followed by oxidativehydrolysis to produce secondary alcohol mixture A 20-liter reactionvessel is charged with 2500 ml. of tetrahydrofuran and 640 g. of sodiumborohydride, and 2800 g. of boron trifluoride etherate is added dropwiseto the mixture. Eighteen hundred and fifty grams of1,4,9,9-tetramethyl-A -octahydro-4J-methanoazulene (beta-patchoulene) isadded to the reaction mass, and the mass is refluxed at atmosphericpressure for eight hours.

After cooling to 25 C., 300 ml. of water is added over a 30-minuteperiod while the mass is maintained at 25 C. Six and three tenths gramsof 3.0 M aqueous sodium hydroxide is then added with stirring during 45minutes. Fifteen hundred ml. of a 50% solution of H is added at 25 C.over 75 minutes. After the addition is complete, the organic layer isseparated, the aqueous phase is extracted twice with equal volumes ofdiethyl ether, and the ether extracts and the organic layer arecombined, washed twice with equal volumes of sodium chloride solutions,dried over anhydrous magnesium sulfate, filtered and concentrated on aflash evaporator. The yield of crude secondary alcohol mixture,containing secondary alcohols of the structure EXAMPLE II Oxidation ofthe secondary alcohol to the ketone A l0-liter reaction vessel ischarged with 888 g. of chromium trioxide, 3.8 liters of glacial aceticacid and 1600 ml. of water. A solution of 2254 g. of the alcohol mixtureprepared in Example I in 2.2 liters of acetic acid is added dropwise tothe mixture, while the temperature is kept at 2530 C. The mixture isstirred until the exotherm ceases.

A solution of 250 g. of chromium trioxide in 600 ml. of glacial aceticacid and 100 ml. of water is then added to the reaction mass. The massis maintained at 25-30 C. with stirring for 12 hours. At this point thereaction is 95% complete as indicated by GLC, and the acetic acidwherein R R and R are as defined above, the ratio of IIzIzIII being70:2l:5. The structures are confirmed by nuclear magnetic resonance(NMR) and infrared (IR) analyses. The mixture is separated and isolated(via GLC- conditions set forth above). Each of the three isomerspossesses strong amber and patchouli fragrance notes, with additionalcamphoraceous notes. IR analysis of the three mixtures yields thefollowing data:

Centimeters II I III 5-membered ring carbonyl Methylene alpha tocarbonyl. gem-Dimethyl. Meth 6-membered ring carbon EXAMPLE IIIHydroboration of beta-patchoulene followed by oxidation in situ A5-liter reaction vessel is charged with 1000 ml. of tetrahydrofuran, g.of sodium borohydride, and 250 g. beta-patchoulene, and 183 g. of borontetrafiuoridediethyl etherate is added- (this being one-half of theamount required to convert all the sodium borohydride to diborane).'Thereaction mass is refluxed at atmospheric pressure for four hours and anadditional 30 g. of boron trifluoride-diethyl etherate is then added tothe mass. The mixture is refluxed again for a period of four hours.

The resulting mixture containing boron addition compounds is subjectedto oxidative hydrolysis and final oxidation to the desired lretone inthe same reaction vessel as follows: A mixture of 1000 g. 93% sulfuricacid 1000 g. water g. sodium dichromate is then added to the reactionmass with stirring, while the mass is maintained at 25 C. Stirring at 25C. is continued GLC (using the parameters set forth in Example II) showsthe reaction to be complete.

The phases are separated and the aqueous phase is extracted twice withequal volumes of diethyl ether. The ether extracts and organic layer arecombined and washed three times with equal volumes of saturated sodiumchloride solution, dried over anhydrous magnesium sulfate and treated ina flash evaporator to remove the diethyl ether. The crude ketone is thenrushed over under good vacuum, and subsequently distilled at 103-144 C.at 0.8 mm. Hg pressure.

GLC (conditions set forth in Example II) indicates three ketones. Thestructures are confirmed by IR and NMR analysis to be the Z-one, 3-one,and 8-one. The ratio of IIzIzIII according to the GLC analysis is30:24:15. The mixture produced has a strong amber,

patchouli, camphoraceous odor with an additional fine woody cigar boxfragrance note. The 2-one and 3-one when separated by GLC have the samefragrance notes as those compounds obtained in Example II. IR analysisof the mixtures yields data identical to those obtained for the mixturesof Example II.

EXAMPLE 1V Pehydro ketones from patchouli alcohol Three and seven-tenthsgrams of patchouli alcohol is dissolved in 3.5 ml. of distilled hexane,and 1.0 g. of cation exchange resin [Amberlite IRC 120(H)CP, achemically pure sulfonated styrene8% divinyl benzene copolymer having anexchange capacity of 1.7 meq./ml. (wet), manufactured by Rohm & Haas Co.of Philadelphia, Pa.] is added to the solution. The mixture is refluxedfor five hours at atmospheric pressure. The ion exchange resin is thenremoved from the reaction mass by filtration and the mass is separatedinto three components using GLC (procedure of Example II):beta-patchoulene, delta patchoulene, and the patchouli alcohol startingmaterial.

Into a 100 m1. three-necked flask equipped with a condenser, nitrogenfeed means, pressure-equilibrated dropping funnel, and magnetic stirringbar are placed the following materials:

123 mg. delta-patchoulene trace zinc chloride 5 ml. anhydrous diethylether 1.0 g. sodium borohydride The reaction mass is cooled to 5 C. and,maintaining this temperature, the mass is stirred for one hour. Borontrifluoride-etherate, 10 ml., diluted with 10 ml. of diethyl ether isadded to the reaction mass over a period of 1 /2 hours, stillmaintaining the mass at 5 C. After stirring for one hour at -5 C., 2 ml.of water is added to destroy any remaining unreacted hydride. To theboron adduct mixture, 5 ml. of 3 M aqueous sodium hydroxide solution isadded. Immediately thereafter, 7 ml. of a 30% H solution is added to thereaction mass during one hour while maintaining the temperature at C.The reaction mass is then stirred at 5 C. for an additional two hours.

The organic phase is separated, and the aqueous phase is successivelyextracted with three 10 ml. volumes of diethyl ether. The ether extractis combined with the organic phase and the combination is then washedsuccessively with three 10 ml. volumes of water, dried over anhydroussodium sulfate, and stripped of diethyl ether. The crude materialchromatographed over silicic acid (5% deactivated, 3 g.) is found to bethe perhydro secondary alcohol.

To 40 mg. of this secondary alcohol dissolved in 2 ml. glacial aceticacid is added 50 mg. of CrO dissolved in 1.5 ml. glacial acetic acid.The mixture is maintained at 0 C., for one hour, diluted with 10 ml. ofwater, and extracted with two successive 10 ml. portions of diethylether. The combined ether extracts are then washed with three 5 ml.portions of 2 N Na CO and three 5 ml. portions of water. The washedether extracts are dried over anhydrous sodium sulfate, and the solventis removed to furnish crude ketone which is purified using the GLCprocedure of Example II.

The purified ketone mixture has an amber, patchouli, camphoraceous odor.IR analysis of the mixture of ketones shows a 5-membered ring moiety at1735 cmf Mass spectral analysis shows a molecular ion at m/e of 220. Themass spectra, IR and NMR analyses confirm I and II.

EXAMPLE V Perhydro ketone from direct oxidation of beta-patchoulene (A)Oxidizing agent preparation: Into a 3-liter reaction flask equipped witha reflux condenser, Y-tube, stirrer and nitrogen purge means is placed1.2 liters of t-butyl alcohol. With nitrogen purging, 400 g. ofanhydrous chromium trioxide is added over one hour. The mass is thendissolved in 2 liters of carbon tetrachloride, washed with three 500 cc.portions of water and dried over anhydrous sodium sulfate.

(B) Direct oxidation: Into a 12-liter reaction flask equipped with areflux condenser, stirrer, Y-tube, thermometer and addition funnel, areintroduced the following materials:

200 g. beta-patchoulene 2 liters carbon tetrachloride cc. aceticanhydride 600 cc. acetic acid- The mass is stirred and heated to 50 C.

A solution consisting of 3 /2 liters of the chromium trioxide-t-butylalcohol complex prepared as in (A) 160 cc. acetic anhydride, and 600 cc.of acetic acid is prepared. This solution is added dropwise to thebetapatchoulene solution over a 2 /2 hour period, while the reactionmass is maintained at 50 C. The reaction mass is stirred for a period of20 hours at 50 C. and washed with a solution of 1.500 g. oxalic aciddissolved in 12 liters of water.

The organic layer is separated from the aqueous phase and washed withtwo 500 cc. portions of water, neutralized with a saturated sodiumcarbonate solution, and washed twice again with two successive 500 cc.portions of water. The washed material is dried over anhydrous sodiumsulfate and concentrated under vacuum.

The crude concentrated material is distilled at 113 148 C. at l.80.8 mm.Hg pressure.

(C) Reduction: The distilled product, 2.5 g., produced by the foregoingdirect oxidation is dissolved in 3 cc. of benzene and 3 cc. of aqueoussaturated NH OH in a 50 cc. three-neck reaction flask equipped with areflux condenser, thermometer, and magnetic stirring bar. The reactionmixture is cooled to 5 C. To the cooled mass, 0.8 g. of sodium particlesare added over one hour. The temperature of the reaction mass ismaintained between 10 and 15 C. After a one-hour period, 3 cc. ofbenzene and 5 cc. of aqueous saturated NH OH are added to the reactionflask. Then 0.8 g. of sodium particles are added over a /2 hour period.The reaction mass is then stirred for 2 hours at 25 C. and stored at 0C. for a period of 13 hours. Two phases thereupon exist in the reactionmass: an organic phase and an aqueous phase.

The organic phase is washed with 5 cc. of a 3.7% solution of HCl andwashed twice with 5 cc. portions of distilled water. The washed organicphase is dried over anhydrous sodium sulfate, and the benzene solvent isremoved with nitrogen. IR analysis indicates that a substantial portionof the ketone is reduced to perhydro secondary alcohol.

(D) Oxidation: The secondary alcohol formed in the immediately precedingsection is dissolved in 9 cc. of glacial acetic acid and cooled to 0 C.To this solution is added a solution consisting of 350 mg. chromiumtrioxide dissolved in 12 cc. of glacial acetic acid and 0.3 ml. ofdistilled water. The reaction mass is stirred and maintained at 0 C.during the addition. The mass is then stirred at 24-25 C. for a periodof one hour.

The reaction mass so obtained is poured into 30 cc. of distilled waterin a 250 cc. separatory funnel and extracted four times with 25 cc.portions of diethyl ether. The ether extracts are combined and washedwith 10% Na CO solution until basic. They are then washed with distilledwater until neutral, dried over anhydrous sodium sulfate, andconcentrated under vacuum. The resulting crude ketone mixture isdistilled at 1l0-140 C. under 0.8 mm. pressure. IR, NMR and massspectral analyses show the presence of I, II and III. The purifiedketone mixture has an amber, patchouli, camphoraceous odor with awoodycigar box note.

1 1 EXAMPLE v1 Perfume composition A perfume composition is preparedwith the following ingredients:

Parts Vetivert oil 40 Ketone mixture of Example II 60 Sandalwood oil 100Rose geranium oil 200 Musk extract (3%) 25 Civet extract (3%) 25Benzyl-iso-Eugenol 100 Coumarin 100 Heliotropin 50 Bois de Rose oil 200Benzoin resin 100 The perfume composition exhibits an excellent woodyfragrance. When the ketone mixture is omitted, the composition lacks thewoody, amber fullness of the complete perfume composition of thisexample.

It will be understood from the present description that I, II and IIIproduced according to the present invention can be used separately or incombination with each other to provide a good intense amber, woodyfragrance note.

EXAMPLE VII The Example H mixture is evaluated against the knownmaterial patchoulione by preparing a solution of each in diethylphthalate and comparing blotter strips containing samples of thesolutions. The patchoulione has a rooty earthy fragrance character,while the Example II material according to the present invention has anamber precious wood fragrance. The Example II material is much moreintense, being at least twice as strong as patchoulione, and maintainsits strength and aroma pattern after several days dryout on the blotterstrips.

In the following examples, the soap base and soap chips used areunperfumed sodium-based toilet soaps made from tallow and coconut oil.The detergent powder is a material obtained from Lever Bros. Co. andsold under the trademark Rinso. The liquid detergent is a productmanufactured by Ultra Chemical Co., and is known as P-87 liquiddetergent.

EXAMPLE VIH Preparation of soap composition One hundred grams of soapchips are mixed with one gram of the perfume composition of Example VIuntil a substantially homogeneous composition is obtained. The perfumedsoap composition manifests an excellent woody, amber, patchouli odorcharacter.

EXAMPLE IX Preparation of a detergent composition A total of 100 gramsof a detergent powder is mixed with 0.15 gram of the perfume compositionof Example VI until a substantially homogeneous composition is obtained.This composition has an excellent woody, amber odor.

EXAMPLE X Preparation of a cosmetic powder composition A cosmetic powderis prepared by mixing in a ball mill grams of talcum powder with 0.25gram of the mixture obtained from the process of Example III. A secondcosmetic powder is similarly prepared except that the mixture of Example[I is used. Both have excellent woody, amber, atchouli-like odors.

EXAMPLE XI Perfumed liquid detergent Concentrated liquid detergents witha woody, amber, patchouli-like odor are prepared containing 0.10%, 0.15%and 0.20% of the 3-one of this invention. They are prepared by addingand homogeneously mixing the appropriate quantity of the compound in theliquid detergent. The detergents all possess a woody amber fragrance,the intensity increasing with greater concentration of the ketone ofthis invention.

What is claimed is:

1. A perfume composition containing a perfume carrier or vehicle and asmall amount of a ketone effective to impart a woody amber fragrancecharacter to the composition, the ketone having the formula whereinoneof R R and R is oxygen and each of the other two represents twohydrogen atoms, or mixture of said ketones.

2. The perfume composition of cltim 1 additionally containing asurface-active agent.

3. The perfume composition of claim 1, additionally containing talcum.

References Cited UNITED STATES PATENTS 3,407,225 10/ 1968 Dunkle 260586A X OTHER REFERENCES Chem. Abs., vol. 51, 1957, pp. 4292f-4293a. Chem.Abs., vol. 44, 1950, pp. 3945c-3947h. Brown: Hydroboration, 1962, pp.214-215.

ALBERT T. MEYERS, Primary Examiner A. P. FAGELSON, Assistant ExaminerUS. Cl. X.R. 42469, 365

g;; g UMTED STATES PATENT omen UERTWMATE or CQ HREQTKON Patent No. 3'748I Dated July 24 1973 James D, Grossman, Braja Do Mookherjee, Inventor(s)Robert Sc, De Simone, and Ernest T. Theimer It is certified that; errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

In the designation of the inventors:

"Crossman" should read Grossman Col.) 2, line 4, "anozulen" should readanoazulen Col 4, line 17, cancel "herewith" 0 Col. 5 lines 30469 p thecorrect formula should read:

Col. 6, line 4, "10 1 should read -be--.

Col. 6, line 62, torrect the spelling of "according".

Col. 12, claim 2, line 1, correct the spelling of "claim" Signed andsealed this 20th day of November 1973.

(SEAL) Attest:

EDWARD I l-FLETCHER, JR. RENE D. TEGTMEYER Attesting Officer ActingCommissioner of Patents

